Surface treatment of plastic material with an organic polymerisable and/or crosslinkable composition having reactive functions

ABSTRACT

The invention concerns a novel method for treating the surface of plastic material comprising the following steps: (1) applying on at least one of the surfaces of the plastic material a composition with polymerisable and/or crosslinkable reactive functions, by cationic process or by cationic and radical process comprising 1 to 99 wt. % of at least a polymerisable and/or at least partly polymerised organic matrix A having oxetane reactive functions (frA); 99 to 1 wt. % of at least a polymerisable and/or at least partly polymerised organic matrix B, including (co) monomers, (co)oligomers and/or (co)polymers selected among those having epoxy (α 1 ) and/or acrylate (α 2 ) and/or alkenyl-ether (α 3 ) and/or hydroxy (α 4 ) reactive functions (frB); an efficient amount of at least a cationic or cationic and radical initiator system C; optionally at least a sensitizer D and at least a pigment E; (2) polymerising and/or crosslinking the treated surface by exposure under an irradiating source and/or under electron beam(s).

[0001] The field of the invention is that of the surface treatment ofplastics based on compositions which can be crosslinked and/orpolymerized under irradiation, in particular under UV irradiation and/orby an electron beam. More specifically, the invention relates to theplastic surface treated for the purpose of forming a coating, such as anink, a nonstick coating, an adhesive coating or a varnish.

[0002] Plastics are increasingly used as packagings, such as containers,in particular cases, bottles and sachets. These plastics can betransparent, translucent, colored or opaque and are generally based onpolyethylene, on polypropylene, on polystyrene and/or on polyester.

[0003] The development of a surface treatment for coating plastics iscomplex and requires specific qualities of adhesion, of robustness, offlexibility, of resistance to scratching, of resistance to twisting, ofresistance to water and of resistance to stains.

[0004] To date, however, technologies, in particular those for thermaldrying of systems often based on products carried in solvents, are notsuitable for efficiently treating plastic surfaces and for retaining, inparticular over time and during the handling thereof, the qualitieswhich are necessary for it.

[0005] The present invention proposes to overcome the existingshortcomings in the field of the surface treatment of plastics. One ofthe essential objectives of the present invention is therefore toprovide a novel process for the surface treatment of plastics with acomposition which can be crosslinked and/or polymerized by the cationicroute or by the cationic and radical route which meet theseexpectations.

[0006] The present invention relates to a novel process for the surfacetreatment of a plastic for the purpose of forming a coating comprisingthe following stages:

[0007] (1) application, to at least one of the surfaces of the plastic,of a composition with reactive functional groups which can bepolymerized and/or crosslinked by the cationic route or by the cationicand radical route comprising:

[0008] 1 to 99% by weight, and preferably 1 to 60% by weight, of atleast one polymerizable and/or at least partially polymerized organicmatrix A comprising (co)monomers, (co)oligomers and/or (co)polymersselected from those having oxetane reactive functional groups (Arf),

[0009] 99 to 1% by weight, and preferably 99 to 40% by weight, of atleast one polymerizable and/or at least partially polymerized organicmatrix B comprising (co)monomers, (co)oligomers and/or (co)polymersselected from those having epoxy (α₁) and/or acrylate (α₂) and/oralkenyl ether (α₃) and/or hydroxyl (α₄) reactive functional groups(Brf),

[0010] an effective amount of at least one cationic or cationic andradical initiator system C,

[0011] optionally at least one sensitizer D,

[0012] and optionally at least one pigment E;

[0013] (2) and polymerization and/or crosslinking of the treated surfaceby its exposure under a source of irradiation and/or under electronbeam(s).

[0014] This novel type of treatment confers on plastics, and moreparticularly polypropylene, appropriate surface qualities as regardsadhesion, robustness, flexibility, resistance to scratching, resistanceto twisting, resistance to water, resistance to stains, absence ofshrinkage in volume and, in particular for transparent coatingsobtained, absence of yellowing.

[0015] The exposure under a source of irradiation is generally carriedout under UV radiation. More particularly, use is made of UV radiationwith a wavelength of the order of 200 to 500 nm.

[0016] The matrix A with oxetane reactive functional groups (Arf) usedwithin the composition according to the process of the invention can bebased on (co)monomers, (co)oligomers and/or (co)polymers of highlyvaried natures. In this respect, the following (co)monomers,(co)oligomers and/or (co)polymers composed of at least one of thefollowing species are particularly suitable:

[0017] A1) monomers with oxetane and alkoxy functional groups, oxetaneand hydroxyl functional groups, or oxetane and alkoxysilyl functionalgroups of formula:

[0018] in which:

[0019] R₁ is (i) a hydrogen atom; (ii) a linear or branched alkylradical comprising from 1 to 30 carbon atoms; (iii) an aryl radicalcomprising from 6 to 30 carbon atoms, which radical is optionallysubstituted by at least one fluorine atom, one carboxyl radical, onehydroxyl radical, one ester radical or one radical with a ketonefunctional group; (iv) a cycloalkyl radical comprising from 5 to 6carbon atoms, which radical is optionally substituted by at least onefluorine atom, one hydroxyl radical, one carboxyl radical, one esterradical or one radical with a ketone functional group; (v) an OR′radical where R′ is a linear or branched alkyl radical comprising from 1to 30 carbon atoms; or (vi) an alkenyl radical comprising from 2 to 12carbon atoms,

[0020] R₂ is (i) a hydrogen atom; (ii) an alkenyl radical comprisingfrom 2 to 12 carbon atoms (for example a vinyl radical or a propenylradical); (iii) a linear or branched alkyl radical comprising from 1 to30 carbon atoms, which radical is optionally substituted, for example byan oxirane group; (iv) an aryl radical comprising from 6 to 30 carbonatoms, which radical is optionally substituted, for example by at leastone alkyl radical comprising from 1 to 30 carbon atoms, one benzylradical, one CF₃ radical, one halogen atom, one hydroxyl radical, onecarboxyl radical or one alkoxy radical; (v) a linear or branchedalkylated and silylated or silylated group —(C_(n)H_(2n))—SiR₃R₄R₅,where n is between 1 and 12 and R₃, R₄ and R₅, which are identical ordifferent, represent a hydrogen atom, a hydroxyl radical or an alkoxyradical OR′ where R′ is a linear or branched alkyl radical comprisingfrom 1 to 30 carbon atoms; (vi) a linear or branched alkyl radicalcomprising from 1 to 30 carbon atoms; (vii) an aryl radical comprisingfrom 6 to 30 carbon atoms, which radical is optionally substituted;(viii) an alkenyl radical comprising from 2 to 12 carbon atoms; (ix) anacrylate radical; (x) a methacrylate radical (for example —CO—CH═CH₂; or(xi) a urethane radical —CO—NH—R₁ in which R₁ has the same definition asthat given above,

[0021] A2) monomers comprising carboxyl and oxetane functional groups orcomprising oxetane and alkoxysilyl functional groups of formula:

[0022] in which:

[0023] R₁ has a definition identical to that given in A1),

[0024] R₂ has a definition identical to that given in A1);

[0025] A3) difunctional oxetane monomers of formula:

[0026] in which:

[0027] m, which is identical or different, is equal to 0 or 1,

[0028] R₁ has a definition identical to that given in A1),

[0029] R₆, a divalent radical, is (i) a linear or branched alkyl radicalcomprising from 1 to 30 carbon atoms; (ii) an aryl radical comprisingfrom 6 to 30 carbon atoms, which radical is optionally substituted (byat least one alkyl radical comprising from 1 to 30 carbon atoms; (iii)an aryl radical comprising from 6 to 30 carbon atoms (for example abenzyl radical); (iv) a cycloalkyl radical comprising from 5 to 30carbon atoms (ex.: cyclohexyl); (v) a —CH₂—C₆H₁₀—CH₂— radical; (vi) a—CH₂—C₆H₄—CH₂— radical; (vii) a CF₃ radical; (viii) a halogen atom; (ix)a hydroxyl radical; (x) a carboxyl radical; (xi) an alkoxy radical OR′where R′ has a definition identical to that given in A1); (xii) a silylgroup ═SiR₃R₄ where n is between 0 and 12 and R₃ and R₄, which areidentical or different, represent a hydrogen atom, a hydroxyl radical,an alkoxy radical OR′ where R′ has a definition identical to that givenin A1), a linear or branched alkyl radical comprising from 1 to 30carbon atoms, an aryl radical comprising from 6 to 30 carbon atoms whichis optionally substituted, a —C₆H₄—C(CH₃)₂—C₆H₄— radical or an alkenylradical comprising from 2 to 12 carbon atoms.

[0030] Mention will be made, as examples of species A1, of those offollowing formulae:

[0031] Mention will be made, as examples of species A2, of those offollowing formulae:

[0032] Mention will be made, as species A3, of those of followingformulae:

[0033] In addition to species of organic nature, the matrix A cancomprise polyorganosiloxanes A4) which are composed of units of formula(II) and are terminated by units of formula (III) or are cyclic and arecomposed of units of formula (II), which formulae are represented below:

[0034] in which:

[0035] the R⁶ and R⁷ symbols, which are alike or different, represent:

[0036] a linear or branched alkyl radical comprising 1 to 8 carbon atomswhich is optionally substituted by at least one halogen, preferablyfluorine, the alkyl radicals preferably being methyl, ethyI, propyl,octyl and 3,3,3-trifluoropropyl,

[0037] a cycloalkyl radical comprising between 5 and 8 cyclic carbonatoms, which radical is optionally substituted,

[0038] an aryl radical comprising between 6 and 12 carbon atoms, whichradical can be substituted, preferably phenyl or dichlorophenyl,

[0039] an aralkyl radical having an alkyl part comprising between 5 and14 carbon atoms and an aryl part comprising between 6 and 12 carbonatoms, which part is optionally substituted on the aryl part byhalogens, alkyls and/or alkoxyls comprising 1 to 3 carbon atoms,

[0040] the Z symbols, which are alike or different, represent:

[0041] an R⁶ and/or R⁷ group,

[0042] a hydrogen radical,

[0043] and/or a crosslinkable oxetane functional group connected to thesilicon of the polyorganosiloxane via a divalent radical which comprisesfrom 2 to 20 carbon atoms and which can comprise at least oneheteroatom, preferably oxygen, it being possible for the latter to bebonded directly to the silicon, forming an ≡Si—OC≡ bond,

[0044] with at least one of the Z symbols representing a crosslinkableoxetane functional group.

[0045] According to an advantageous alternative form of the invention,the polyorganosiloxanes A4 used comprise from 1 to 10 organofunctionalgroups per macromolecular chain.

[0046] These linear polyorganosiloxanes can be oils with a dynamicviscosity at 25° C. of the order of 10 to 10 000 mPa.s at 25° C.,generally of the order of 20 to 5000 mPa.s at 25° C. and more preferablystill of 20 to 600 mPa.s at 25° C., or gums exhibiting a molecular massof the order of 1 000 000.

[0047] When the polyorganosiloxanes are cyclic polyorganosiloxanes, thelatter are composed of units (II) which can, for example, be of thedialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiloxanesexhibit a viscosity of the order of 1 to 5000 mPa.s.

[0048] Mention may be made, as examples of an organofunctional radicalof the oxetane type connected to the backbone of the polyorganosiloxaneA4, of the group of following formula:

[0049] The oxetane functional polyorganosiloxanes can be prepared byhydrosilylation of unsaturated oxetanes or condensation of oxetanesincluding a hydroxyl functional group.

[0050] The polyorganosiloxanes A4 corresponding best to the subjectmatter of the invention are described in the formulae below. X canrepresent an alkyl, cyclohexyl, trifluoropropyl, perfluoroalkyl, alkoxyor hydroxypropyl group and R can represent a C₁ to C₁₀ alkyl,cyclohexyl, trifluoropropyl or C₁ to C₁₀ perfluoroalkyl radical and(0≦a≦1 000); (1≦b≦1 000);

[0051] As regards the matrix B, the latter can comprise in particular atleast one of the following organic species B1:

[0052] α_(1.1)) cycloaliphatic epoxides and in particular:

[0053] epoxides of the 3,4-epoxycyclohexylmethyl3′,4′-epoxycyclohexanecarboxylate type:

[0054] or bis(3,4-epoxycyclohexyl) adipate;

[0055] α_(1.2)) noncycloaliphatic epoxides and in particular:

[0056] epoxides of the type of those resulting from the condensation ofbisphenol A and of epichlorohydrin and of the type:

[0057] di- and triglycidyl ethers of bisphenol A alkoxylated with1,6-hexanediol, with glycerol, with neopentyl glycol and withtrimethylolpropane,

[0058] or diglycidyl ethers of bisphenol A,

[0059] α-olefin epoxides, novolac epoxides, epoxidized soybean oil,epoxidized linseed oil and epoxidized polybutadiene,

[0060] α₂) acrylates, and in particular:

[0061] epoxidized acrylates, preferably the oligomer of bisphenol Aepoxydiacrylate (Ebecryl 600),

[0062] polyester glycerol acrylates, preferably a mixture of oligomer ofacrylate which is trifunctional obtained from glycerol and polyester(Ebecryl 810),

[0063] multifunctional acrylates, preferably pentaerythritol triacrylate(PETA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanedioldiacrylate (HDODA), trimethylolpropane ethoxylate triacrylate,thiodiethylene glycol diacrylate, tetraethylene glycol diacrylate(TTEGDA), tripropylene glycol diacrylate (TRPGDA), triethylene glycoldiacrylate (TREGDA), trimethylpropane trimethacrylate (TMPTMA),dipentaerythritol pentaacrylate and pentaerythritol ethoxylatetetraacrylate,

[0064] urethane acrylates,

[0065] polyether acrylates,

[0066] polyester acrylates,

[0067] unsaturated polyesters,

[0068] acrylic acrylates,

[0069] α₃) linear or cyclic alkenyl ethers and in particular:

[0070] vinyl ethers, in particular dodecyl vinyl ether (DDVE),cyclohexyl vinyl ether (CVE), butanediol divinyl ether (BDVE),butanediol monovinyl ether (HBVE), cyclohexanedimethanol divinyl ether(CHDVE), cyclohexanedimethanol monovinyl ether (CHMVE), triethyleneglycol divinyl ether (DVE-3) and vinyl ethers of formula:

[0071] propenyl ethers,

[0072] and butenyl ethers;

[0073] α₄) polyols, and preferably the compound of formula:

[0074] In addition to organic species B1, the matrix B can also comprisemonomer(s), (co)oligomer(s) and/or (co)polymer(s) of polyorganosiloxanenature B2, which monomer(s), (co)oligomer(s) and/or (co)polymer(s) arecomposed of units of formula (IV) and are terminated by units of formula(V) or are cyclic and are composed of units of formula (IV), whichformulae are represented below:

[0075] in which:

[0076] the R⁶ and R⁷ symbols, which are alike or different, havedefinitions identical to those given for A4,

[0077] the Z′ symbols, which are alike or different, represent:

[0078] an R⁶ and/or R⁷ group,

[0079] a hydrogen radical,

[0080] and/or a crosslinkable organofunctional group, preferably anepoxy functional, dioxolane functional and/or alkenyl ether functionalgroup, connected to the silicon of the polyorganosiloxane via a divalentradical which comprises from 2 to 20 carbon atoms and which can compriseat least one heteroatom, preferably oxygen,

[0081] with at least one of the Z′ symbols representing a crosslinkableorganic functional group.

[0082] According to an advantageous alternative form of the invention,the polyorganosiloxanes B2 used comprise from 1 to 10 organofunctionalgroups (Brf) per macromolecular chain. For an epoxy functional group,this corresponds to epoxide levels varying from 20 to 2 000 molarmeq/100 g of polyorganosiloxane.

[0083] The linear polyorganosiloxanes B2 can be oils with a dynamicviscosity at 25° C. of the order of 10 to 10 000 mPa.s at 25° C.,generally of the order of 20 to 5 000 mPa.s at 25° C. and morepreferably still of 20 to 600 mPa.s at 25° C., or gums exhibiting amolecular mass of the order of 1 000 000.

[0084] In the case of cyclic polyorganosiloxanes B2, the latter arecomposed of units (IV) which can, for example, be of the dialkylsiloxyor alkylarylsiloxy type. These cyclic polyorganosiloxanes exhibit aviscosity of the order of 1 to 5 000 mPa.s.

[0085] Mention may be made, as examples of organofunctional groups (Brf)of the epoxy type connected to the polyorganosiloxane backbone B2, ofthose of following formulae:

[0086] As regards the organofunctional groups (Brf) of the alkenyl ethertype connected to the polyorganosiloxane backbone B2, mention may bemade of those present in the following formulae:

O)_(n′)—(CH₂)_(n″)—O—CH═CH₂

—(O)_(n′)—(CH₂)_(n″)—R⁸—O—CH═CH₂

—(O)_(n′)—(CH₂)_(n″)—O—CH═CH—R⁹

[0087] in which:

[0088] n′ represents 0 or 1 and n″ an integer between 1 and 5

[0089] R⁸ represents:

[0090] a linear, branched or cyclic C₁-C₁₂ alkylene radical which isoptionally substituted,

[0091] or a C₅-C₁₂ arylene radical, preferably a phenylene radical,which is optionally substituted, preferably by one to three C₁-C₆ alkylgroups,

[0092] R⁹ represents a linear or branched C₁-C₆ alkyl radical.

[0093] As regards the organofunctional dioxolane groups (Brf) alkenylether connected to the polyorgano-siloxane backbone B2, mention may bemade of those present in the following formulae:

[0094] The polyorganosiloxanes B2 with epoxy, dioxolane or alkenyl etherfunctional groups (Brf) are generally provided in the form of fluidsexhibiting a viscosity at 25° C. of 10 to 10 000 mm²/s and preferably of20 to 600 mm²/s.

[0095] The dynamic viscosity at 25° C. of all the silicones consideredin the present description can be measured using a Brookfieldviscometer, according to Standard AFNOR NFT 76 102 of February 1972.

[0096] The alkenyl ether functional polyorgano-siloxanes B2 can beprepared by a hydrosilylation reaction between oils comprising Si—Hunits and vinyloxy functional compounds, such as allyl vinyl ether orallylvinyloxyethoxybenzene.

[0097] The epoxy functional polyorganosiloxanes B2 can be prepared by ahydrosilylation reaction between oils comprising Si—H units and epoxyfunctional compounds, such as 4-vinylcyclohexene oxide, allyl glycidylether, and the like.

[0098] The dioxolane functional polyorganosiloxanes B2 can be preparedby hydrosilylation of unsaturated dioxolanes.

[0099] The polyorganosiloxanes B2 corresponding best to the subjectmatter of the invention are described in the formulae hereinbelow andhave at least one epoxide, alkenyl ether or oxetane group. X canrepresent an alkyl, cyclohexyl, trifluoropropyl, perfluoroalkyl, alkoxyor hydroxypropyl group, R can represent a C₁ to C₁₀ alkyl, cyclohexyl,trifluoropropyl or C₁ to C₁₀ perfluoroalkyl radical and (0≦a≦1 000);(1≦b≦1 000).

[0100] The initiation of the polymerization and/or crosslinking stageaccording to the invention is carried out by virtue of the presence ofthe initiator system C, which is either cationic or cationic andradical.

[0101] The cationic initiators can be chosen from onium borates (takenon their own or as a mixture of them), the onium being that of anelement from Groups 15 to 17 of the Periodic Table [Chem. & Eng. News,Vol. 63, No. 5, 26, of Feb. 4, 1985], or borates of an organometalliccomplex of an element from Groups 4 to 10 of the Periodic Table [samereference].

[0102] The cationic entity of the cationic initiator is selected from atleast one of the following species:

[0103] 1) onium salts of formula (VI):

[(R¹⁰)_(n)-A-(R¹¹)_(m)]⁺  (VI)

[0104] in which:

[0105] A represents an element from Groups 15 to 17, such as, forexample: I, S, Se, P or N,

[0106] R¹⁰ represents a C₆-C₂₀ carbocyclic or heterocyclic aryl radical,it being possible for said heterocyclic radical to comprise nitrogen orsulfur as heteroelements,

[0107] R¹¹ represents R¹⁰ or a linear or branched C₁-C₃₀ alkyl oralkenyl radical; said R¹⁰ and R¹¹ radicals optionally being substitutedby a C₁-C₂₅ alkoxy, C₁-C₂₅ alkyl, nitro, chloro, bromo, cyano, carboxyl,ester or mercapto group,

[0108] n is an integer ranging from 1 to v+1, v being the valency of theelement A,

[0109] m is an integer ranging from 0 to v−1, with n+m=v+1,

[0110] 2) the oxoisothiochromanium salts disclosed in patent applicationWO 90/11303, in particular the sulfonium salt of2-ethyl-4-oxoisothiochromanium or of 2-dodecyl-4-oxoisothiochromanium,

[0111] 3) sulfonium salts in which the cationic entity comprises:

[0112] 3₁ at least one polysulfonium species of formula VIII.1:

[0113] in which:

[0114] the Ar¹ symbols, which are identical or different, each representa monovalent aromatic radical (for example: phenyl or naphthyl)optionally substituted with one or more radicals chosen from: (i) alinear or branched C₁-C₁₂, preferably C₁-C₆, alkyl radical, (ii) alinear or branched C₁-C₁₂ alkoxy radical optionally substituted by an—OH group, preferably a C₁-C₆ alkoxy radical, (iii) a halogen atom, (iv)an —OH group, (v) a —COOH group, (vi) a —COO-alkyl ester group, wherethe alkyl part is a linear or branched C₁-C₁₂, preferably C₁-C₆,residue, and (vii) a group of formula —Y⁴—Ar², where the Y⁴ and Ar²symbols have the meanings given immediately below,

[0115] the Ar² symbols, which are identical or different, each representa monovalent aromatic radical (for example: phenyl or naphthyl)optionally substituted with one or more radicals chosen from: (i) alinear or branched C₁-C₁₂ alkyl radical optionally substituted by an —OHgroup, preferably a C₁-C₆ alkyl radical, (ii) a linear or branchedC₁-C₁₂, preferably C₁-C₆, alkoxy radical, (iii) a halogen atom, (iv) an—OH group, (v) a —COOH group, (vi) a —COO-alkyl ester group, where thealkyl part is a linear or branched C₁-C₁₂, preferably C₁-C₆, residue,

[0116] the Ar³ symbols, which are identical or different, each representa divalent phenylene or naphthalene radical optionally substituted withone or more radicals chosen from: (i) a linear or branched C₁-C₁₂,preferably C₁-C₆, alkyl radical, (ii) a linear or branched C₁-C₁₂,preferably C₁-C₆, alkoxy radical, (iii) a halogen atom, (iv) an —OHgroup, (v) a —COOH group, (vi) a —COO-alkyl ester group, where the alkylpart is a linear or branched C₁-C₁₂, preferably C₁-C₆, residue,

[0117] t is an integer equal to 0 or 1, with the additional conditionsaccording to which:

[0118] when t=0, the Y symbol is then a Y¹ monovalent radicalrepresenting the group of formula:

[0119] where the Ar¹ and Ar² symbols have the meanings given above,

[0120] when t=1:

[0121] on the one hand, the Y symbol is then a divalent radical havingthe following meanings y² to Y⁴:

[0122] Y²: a group of formula:

[0123] where the Ar² symbol has the meanings given above,

[0124] Y³: a single valency bond,

[0125] Y⁴: a divalent residue chosen from:

[0126] a linear or branched C₁-C₁₂, preferably C₁-C₆, alkylene residueand a residue of formula —Si(CH₃)₂O—,

[0127] on the other hand, solely in the case where the Y symbolrepresents Y³ or Y⁴, the Ar¹ and Ar² (terminal) radicals have, inaddition to the meanings given above, the possibility of being connectedto one another via the Y′ residue consisting of Y′¹, a single valencybond, or of Y′², a divalent residue chosen from the residues cited withrespect to the definition of Y⁴, which is inserted between the carbonatoms, facing each other, situated on each aromatic ring in the orthoposition with respect to the carbon atom connected directly to the S⁺cation;

[0128] 3₂ at least one monosulfonium species having a single S⁺ cationiccenter per mole of cation and comprising, in the majority of cases,species of formulae:

[0129] in which formula Ar¹ and Ar² have the meanings given above withrespect to the formula (VIII.1), including the possibility of directlyconnecting between them only one of the Ar¹ radicals to Ar² according tothe manner indicated above with respect to the definition of theadditional condition in force when t=1 in the formula (II) involving theY′ residue;

[0130] 3₃ and/or at least one monosulfonium species having a single S⁺cationic center per mole of cation and of formulae:

[0131] in which R₁₄, R₁₅ and R₁₆, which are identical or different,represent (i) a hydrogen atom, (ii) a halogen atom (for example:fluorine), (iii) a linear or branched C₁-C₃₀ alkyl radical which can besubstituted by at least one halogen (for example fluorine), (iv) an —OHradical, (v) an —O—C(═O)—R radical where R is a linear or branchedC₁-C₃₀ alkyl radical which can be substituted by at least one halogen(for example fluorine), (vi) an OR′ alkoxy radical where R′ is a linearor branched C₁-C₃₀ alkyl radical which can be substituted by at leastone halogen (for example fluorine),

[0132] 4) the sulfoxonium salts S⁺═O corresponding to the sulfoniumsalts 3) described above in paragraph 3),

[0133] 5) organometallic salts of formula (IX):

(L¹L²L³M)^(q+)  (IX)

[0134] in which formula:

[0135] M represents a metal from the Group 4 to 10, in particular iron,manganese, chromium or cobalt,

[0136] L¹ represents 1 ligand bonded to the metal M via π electrons,which ligand is chosen from η³-alkyl, η⁵-cyclopendadienyl andη⁷-cycloheptratrienyl ligands and η⁶-aromatic compounds chosen fromoptionally substituted η⁶-benzene ligands and compounds having from 2 to4 condensed rings, each ring being capable of contributing to thevalency layer of the metal M via 3 to 8 π electrons;

[0137] L² represents a ligand bonded to the metal M via π electrons,which ligand is chosen from η⁷-cycloheptatrienyl ligands and η⁶-aromaticcompounds chosen from optionally substituted η⁶-benzene ligands andcompounds having from 2 to 4 condensed rings, each ring being capable ofcontributing to the valency layer of the metal M via 6 or 7 π electrons;

[0138] L³ represents from 0 to 3 identical or different ligands bondedto the metal M via σ electrons, which ligand(s) is (are) chosen from COand NO₂ ⁺; the total electronic charge q of the complex to which L¹, L²and L³ and the ionic charge of the metal M contribute being positive andequal to 1 or 2.

[0139] The borate anionic entity of the cationic initiator has theformula (X):

[BX″_(a)R¹² _(b)]⁻  (X)

[0140] in which:

[0141] a and b are integers ranging from 0 to 3 for a and from 1 to 4for b, with a+b=4,

[0142] the X″ symbols represent:

[0143] a halogen atom (chlorine or fluorine) with a=0 to 3,

[0144] an OH functional group with a=0 to 2,

[0145] the R¹² symbols, which are identical or different, represent:

[0146] a phenyl radical substituted by at least one electron-withdrawinggroup, such as, for example, OCF₃, CF₃, NO₂ or CN, and/or by at least 2halogen atoms (very particularly fluorine), this being when the cationicentity is an onium of an element from Groups 15 to 17,

[0147] a phenyl radical substituted by at least one electron-withdrawingelement or group, in particular a halogen atom (very particularlyfluorine), CF₃, OCF₃, NO₂ or CN, this being when the cationic entity isan organometallic complex of an element from Groups 4 to 10,

[0148] an aryl radical comprising at least two aromatic nuclei, such as,for example, biphenyl or naphthyl, which is optionally substituted by atleast one electron-withdrawing element or group, in particular a halogenatom (very particularly fluorine), OCF₃, CF₃, NO₂ or CN, whatever thecationic entity.

[0149] According to a first preferred form, the cationic initiator ischosen from the onium salts of a cationic entity of formula (VI) and ofan anionic entity of formula (X).

[0150] According to a second preferred form, the cationic initiator ischosen more specifically from the initiator subclasses describedhereinbelow.

[0151] Thus, the borate anionic entity is preferably chosen from anionsof formula [BF_(a)R¹² _(b)]⁻ in which the R¹² symbols, which areidentical or different, represent a phenyl radical substituted by atleast one electron-withdrawing group chosen from OCF₃, CF₃, NO₂ and CNand/or by at least two fluorine atoms.

[0152] More specifically, the anions which are very particularlysuitable are the following: 1′: [B(C₆F₅)₄]⁻ 2′: [(C₆F₅)₂BF₂]⁻ 3′:[B(C₆H₄CF₃)₄]⁻ 4′: [B(C₆F₄OCF₃)₄]⁻ 5′: [B(C₆H₃(CF₃)₂)₄]⁻ 6′:[B(C₆H₃F₂)₄]⁻ 7′: [C₆F₅BF₃]⁻

[0153] As regards the cationic entity of the initiator which can inparticular be associated with a borate anionic entity and in particularwith a borate anionic entity of formula [BF_(a)R¹² _(b)]⁻, five familiesare distinguished:

[0154] 1) onium salts of formula (VI),

[0155] 2) oxoisothiochromanium salts of formula (VII),

[0156] 3) mono- and/or polysulfonium salts, in particular of formulae(VIII.1) to (VIII.5),

[0157] 4) sulfoxonium salts,

[0158] 5) and organometallic salts of formula (IX).

[0159] The first family 1) is disclosed in numerous documents, inparticular in patents U.S. Pat. Nos. 4,026,705, 4,032,673, 4,069,056,4,136,102 and 4,173,476. The following cations will very particularly befavored among these: [C₈H₁₇—O-Φ-I-Φ-CH₃]⁺ [(Φ-CH₃)₂I]⁺[C₁₂H₂₅-Φ-I-Φ-C(CH₃)₃]⁺ [(C₈H₁₇—O-Φ)₂I]⁺ [(C₈H₁₇—O-Φ-I-Φ)]⁺ [(CH₃Φ)₃S]⁺[(CH₃Φ)₂-S-Φ-O—C₈H₁₇]⁺ [(CH₃-Φ-I-Φ-CH(CH₃)₂]⁺ [(CH₃Φ-S-Φ-S-(ΦCH₃)₂]⁺[(C₁₂H₂₅-Φ)₂I]⁺ [(CH₃-Φ-I-Φ-OC₂H₅]⁺ [C₁₂H₂₅-Φ-I-Φ-CH₃]⁺and[(CH₃)₃C-Φ-I-Φ-C(CH₃)₃]⁺

[0160] As regards the second family 2) of cationic entities of formula(VII) and of oxoisothiochromanium type, it preferably comprises cationscorresponding to the structure D₁ which is defined on page 14 ofapplication WO-A-90/11303 and has the formula (VII):

[0161] where the R¹³ radical has the meaning given in this WOapplication with respect to the R¹ symbol; a cationic entity of thistype which is more preferred is that where R¹³ represents a linear orbranched C₁-C₂₀ alkyl radical. Mention will particularly be made, asoxoisothiochromanium salts which are particularly well suited, of thesulfonium salt of 2-ethyl-4-oxoisothiochromanium or of2-dodecyl-4-oxoisothiochromanium.

[0162] As regards the cationic sulfonium entities of the family 3), itwill be specified that the cationic entity preferably comprises at leastone of the following species:

[0163] As regards the fifth type of cationic entity (IX), it is founddisclosed in patent U.S. Pat. Nos. 4,973,722 and 4,992,572 and Europeanpatent applications EP-A-203 829, EP-A-323 584 and EP-A-354 181. Theorganometallic salts more readily used in practice are in particular:

[0164] (η⁵-cyclopentadienyl) (η⁶-toluene)Fe⁺,

[0165] (η⁵-cyclopentadienyl) (η⁶-1-methyl-naphthalene)Fe⁺,

[0166] (η⁵-cyclopentadienyl) (η⁶-cumene)Fe⁺,

[0167] bis(η⁶-mesitylene)Fe⁺,

[0168] bis(η⁶-benzene)Cr⁺.

[0169] Mention will be made, as examples of preferred initiators of theonium borates type, of the following products:

[C₈H₁₇—O-Φ-I-Φ-CH₃]⁺ [B(C₆F₅)₄]⁻

[C₁₂H₂₅-Φ-I-Φ(CH₃)]⁺ [B(C₆F₅)₄]⁻

[(C₈H₁₇)—O-Φ-I-ΦCH(CH₃)₂]⁺ [B(C₆F₅)₄]⁻

[(CH₃Φ)₂S-Φ-O—C₈H₁₇]⁺ [B(C₆H₄CF₃)₄]⁻

[(CH₃Φ)₃S]⁺ [B(C₆H₃(m-CF₃)₂)₄]⁻

[(CH₃Φ)₃S]⁺ [B(C₆H₃(m-CF₃)₂)₄]⁻

[CH₃-Φ-I-Φ-CH(CH₃)₂]⁺ [B(C₆F₅)₄]⁻

(C₈H₁₇)—O-Φ-I-Φ(C₁₂H₂₅)]⁺ [B(C₆F₅)₄]⁻

[(C₈H₁₇—O-Φ)₂I]⁺ [B(C₆F₅)₄]⁻

[(CH₃Φ)₃S]⁺ [B(C₆F₅)₄]⁻

[(C₁₂H₂₅-Φ)₂I]⁺ [B(C₆F₅)₄]⁻

[(Φ-CH₃)₂I]⁺ [B(C₆F₅)₄]⁻

[CH₃-Φ-I-Φ-CH(CH₃)₂]⁺ [B(C₆F₅)₄]⁻

[0170]

[0171] (η⁵-cyclopentadienyl) (η⁶-toluene)Fe⁺[B(C₆F₅)₄]⁻

[0172] (η⁵-cyclopentadienyl) (η⁶-1-methylnaphthalene)Fe⁺[B(C₆F₅)₄]⁻

[0173] and (η⁵-cyclopentadienyl) (η⁶-cumene)Fe⁺[B(C₆F₅)₄]⁻.

[0174] Mention may be made, as other literature reference in definingthe onium borates 1) and the oxoisothiochromanium borates 2) and theborates of organometallic salts 5), which are selected as initiator inthe context of the invention, of the entire contents of patentapplications EP 562 897 and EP 562 922. These contents are incorporatedin full by reference in the present account.

[0175] Mention may be made, as other example of an onium salt which canbe used within the initiator system C, of those disclosed in U.S. Pat.Nos. 4,138,255 and 4,310,469 (Crivello).

[0176] Use may also be made of other cationic initiators; e.g. thosesold by Union Carbide (photo-initiator 6990 and 6974 triarylsulfoniumhexafluorophosphate and hexafluoroantimonate), iodoniumhexafluorophosphate or hexafluoroantimonate salts, or the ferroceniumsalts of these various anions.

[0177] The radical initiators capable of being used within the initiatorsystems C are based on benzophenones. Mention may be made, by way ofexamples, of those sold by Ciba-Geigy: Irgacure 184, Irgacure 500,Darocure 1173, Irgacure 1700, Darocure 4265, Irgacure 907, Irgacure 369,Irgacure 261, Irgacure 784 DO, Irgacure 2959 and Irgacure 651.

[0178] The radical initiators can comprise one or more phosphorus atoms,such as those sold by Ciba-Geigy (Irgacure 1700) or BASF (Lucirin TPO).

[0179] The initiator system C is advantageously employed in solution inan organic solvent (accelerator), preferably chosen from proton donorsand more preferably still from the following groups: isopropyl alcohols,benzyl alcohols, diacetone alcohol, butyl lactate and their mixtures.The photoinitiator C can also be employed directly by dissolving in thematrix A and/or B.

[0180] The term “effective amount of initiator system” is understood tomean, within the meaning of the invention, the amount sufficient toinitiate the crosslinking. This effective amount advantageouslycorresponds to 1×10⁻⁶ to 1, preferably from 1×10⁻⁵ to 1×10⁻¹ and morepreferably still from 1×10⁻⁴ to 1×10⁻² mol of initiator system per 1 molof Arf and Brf.

[0181] The treatment composition according to the invention can alsocomprise at least one (photo)-sensitizer D. This is because, to overcomepossible disadvantages related to the structure of the plastics, to thetreatment composition according to the invention, to the type ofactivation used and/or to the intrinsic inhibiting properties of certainpackagings (thick coating and/or plastic, coating and/or plastic withpigments and the like), the use of a (photo)-sensitizer D proves to bevery beneficial.

[0182] By way of examples, the photosensitizer D can be selected from(poly)aromatic products, which are optionally metallic, and heterocyclicproducts and preferably chosen from the list of following products:phenothiazine, tetracene, perylene, anthracene, 9,10-diphenylanthracene,thioxanthone, 2-chlorothioxanthen-9-one,1-chloro-4-propoxy-9H-thioxanthen-9-one, isopropyl-OH-thioxanten-9-one,mixture of 2- and 4-isomers, 2-isopropyl-9H-thioxanthen-9-one,benzophenone, [4-(4-methylphenylthio)phenyl]phenyl-methanone,4-benzyl-4′-methyldiphenyl sulfide, acetophenone, xanthone, fluorenone,anthraquinone, 9,10-dimethylanthracene,2-ethyl-9,10-dimethyloxyanthracene, 2,6-dimethylnaphthalene,2,5-diphenyl-1,3,4-oxadiazole, xanthopinacol, 1,2-benzanthracene,9-nitroanthracene, and their mixtures.

[0183] Mention will be made, among the pigments E capable of beingpresent within the treatment composition, of, for example, the followingproducts: titanium dioxide, kaolin, calcium carbonate, black iron oxide,nitrogenous barium salts, aluminum pigments, calcium borosilicate,carbanzole violet, azo pigments, red iron oxide, yellow iron oxide,diazo, naphthol, carbon black, bayrite, dianisidine, monoarylide,pyrazolone, toluidine, calcium red, nitrogenous Ca salts, nitrogenous Basalts, diarylide, monoarylide, phthalocyanine, benzimidazoline, bronzepowder or rhodamine.

[0184] Other additives can also be used. Mention may be made, by way ofexamples, of dyes, fillers (silicone or nonsilicone), surfactants,inorganic reinforcing fillers (siliceous or nonsiliceous), bactericides,corrosion inhibitors, binding bases, organosilicon compounds or epoxidecompounds, such as alkoxysilanes, epoxycycloaliphatic compounds orepoxyetheraliphatic compounds.

[0185] In addition to the various components cited-previously, thecompositions of the treatment process according to the invention cancomprise a stabilization additive based on a tertiary, secondary orprimary aliphatic amine and preferably chosen from the derivativesdisclosed in patent application WO98/07798.

EXAMPLES

[0186] The examples which follow will make possible a betterunderstanding of the invention and will make it possible to bring outall its advantages and to glimpse some of its alternative embodiments.

Example 1

[0187] A control formulation respectively comprises, by mass:

[0188] 56.86% of Cyracure® 6105 (Union Carbide),

[0189] 11.20% of Cyracure®TON201 (Union Carbide),

[0190] 30.00% of titanium dioxide R960® (Dupont de Nemours),

[0191] 01.17% of spreading agent Byk 361® (Byk Chemie),

[0192] 0.73% of Rhodorsil® Photoiniator 2074 (Rhodia Silicones),

[0193] and 0.04% of diethylthioxanthone (Lambson).

Example 2

[0194] A formulation according to the invention respectively comprises,by mass:

[0195] 46.71% of Cyracure® 6105 (Union Carbide),

[0196] 08.10% of Cyracure®TON201 (Union Carbide),

[0197] 30.00% of titanium dioxide R960® (Dupont R960),

[0198] 13.50% of 3-ethyl-3-(hydroxymethyl)oxetane (Toa-Gosei),

[0199] 0.92% of spreading agent Byk 361® (Byk Chemie),

[0200] 0.73% of Rhodorsil® Photoiniator 2074 (Rhodia Silicones),

[0201] and 0.04% of diethylthioxanthone (Lambson).

Tests for Examples 1 and 2

[0202] Each formulation is applied in a proportion of 10 g/m² totransparent polypropylene plaques with a thickness of 500 μm positionedhorizontally.

[0203] Polymerization is carried out by irradiation using a 180 W/cmHg/Ga lamp from IST at a rate of 50 m/min.

[0204] The adhesion is evaluated by measuring the attachment of thepolymerized formulation according to a standardized “right-angle latticepattern” test according to Standard EN ISO 2409. A value of 0corresponds to perfect adhesion and a value of 5 corresponds to zeroadhesion.

Results for Examples 1 and 2

[0205] The polymerized formulation of Example 1 does not adhere to thepolypropylene plaque (value equal to 5 according to Standard EN ISO2409).

[0206] In contrast, the attachment of the polymerized formulation ofExample 2 is of very good quality (value equal to 0 according toStandard EN ISO 2409).

Example 3

[0207] A photocrosslinkable formulation for a nonstick coating includinga phthalocyanine blue pigment of Sunfast Blue 15:30 type is preparedaccording to the procedure below.

[0208] A concentrated pigment base CPB is obtained by dispersion of 238parts of phthalocyanine blue and 480 parts of cycloaliphatic epoxidesilicone of formula S1 where a=70 and b=7:

[0209] in a reactor with a capacity of 2 liters equipped with a centralthree-bladed stirrer.

[0210] After mixing for 30 minutes, the concentrated pigment base CPB ismilled on a three-roll mill so as to obtain a dispersion with a midnightblue color and with a particle size of less than 10 μm.

[0211] Subsequently, the following are added and mixed with 10 parts byweight of concentrated pigment base:

[0212] 190 parts of silicone S1,

[0213] 5 parts of 3-ethyl-3-(2-ethylhexylomethyl)oxetane,

[0214] 2 parts of initiator of Rhodorsil® Photoinitiator 2074 type(Rhodia Silicones),

[0215] and 1 part of diethyl-2-thioxanthone.

Tests and Results for Example 3

[0216] The quality of the nonstick coating is evaluated on a UV devicefrom IST equipped with two 200 W/cm Hg lamps doped with Ga on apolypropylene plaque (thickness of 500 micrometers).

[0217] The formulation is polymerized over a thickness of twomicrometers at a rate of 50 m/min.

[0218] The adhesion of the coating to the polypropylene plaque,evaluated by measuring the attachment to the support, is considered tobe excellent.

[0219] The release force for a tesa 4970 adhesive according to StandardFinat10 is 8 g/cm.

1. A process for the surface treatment of a plastic comprising thefollowing stages: (1) application, to at least one of the surfaces ofthe plastic, of a composition with reactive functional groups which canbe polymerized and/or crosslinked comprising: 1 to 99% by weight, andpreferably 1 to 60% by weight, of at least one polymerizable and/or atleast partially polymerized organic matrix A comprising (co)monomers,(co)oligomers and/or (co)polymers composed of at least one of thefollowing species: A1) monomers with oxetane and alkoxy functionalgroups, oxetane and hydroxyl functional groups, or oxetane andalkoxysilyl functional groups of formula:

in which: R₁ is (i) a hydrogen atom; (ii) a linear or branched alkylradical comprising from 1 to 30 carbon atoms; (iii) an aryl radicalcomprising from 6 to 30 carbon atoms, which radical is optionallysubstituted by at least one fluorine atom, one carboxyl radical, onehydroxyl radical, one ester radical or one radical with a ketonefunctional group; (iv) a cycloalkyl radical comprising from 5 to 6carbon atoms, which radical is optionally substituted by at least onefluorine atom, one hydroxyl radical, one carboxyl radical, one esterradical or one radical with a ketone functional group; (v) an OR′radical where R′ is a linear or branched alkyl radical comprising from 1to 30 carbon atoms; or (vi) an alkenyl radical comprising from 2 to 12carbon atoms, R₂ is (i) a hydrogen atom; (ii) an alkenyl radicalcomprising from 2 to 12 carbon atoms (for example a vinyl radical or apropenyl radical); (iii) a linear or branched alkyl radical comprisingfrom 1 to 30 carbon atoms, which radical is optionally substituted, forexample by an oxirane group; (iv) an aryl radical comprising from 6 to30 carbon atoms, which radical is optionally substituted, for example byat least one alkyl radical comprising from 1 to 30 carbon atoms, onebenzyl radical, one CF₃ radical, one halogen atom, one hydroxyl radical,one carboxyl radical or one alkoxy radical; (v) a linear or branchedalkylated and silylated or silylated group —(C_(n)H_(2n))—SiR₃R₄R₅,where n is between 0 and 12 and R₃, R₄ and R₅, which are identical ordifferent, represent a hydrogen atom, a hydroxyl radical or an alkoxyradical OR′ where R′ is a linear or branched alkyl radical comprisingfrom 1 to 30 carbon atoms; (vi) a linear or branched alkyl radicalcomprising from 1 to 30 carbon atoms; (vii) an aryl radical comprisingfrom 6 to 30 carbon atoms, which radical is optionally substituted;(viii) an alkenyl radical comprising from 2 to 12 carbon atoms; (ix) anacrylate radical; (x) a methacrylate radical (for example —CO—CH═CH₂);or (xi) a urethane radical —CO—NH—R₁ in which R₁ has the same definitionas that given above; A2) monomers comprising carboxyl and oxetanefunctional groups or comprising oxetane and alkoxysilyl functionalgroups of formula:

in which: R₁ has a definition identical to that given in A1), R₂ has adefinition identical to that given in A1); A3) difunctional oxetanemonomers of formula:

in which: m, which is identical or different, is equal to 0 or 1, R₁ hasa definition identical to that given in A1), R₆, a divalent radical, is(i) a linear or branched alkyl radical comprising from 1 to 30 carbonatoms; (ii) an aryl radical comprising from 6 to 30 carbon atoms, whichradical is optionally substituted (by at least one alkyl radicalcomprising from 1 to 30 carbon atoms); (iii) an aryl radical comprisingfrom 6 to 30 carbon atoms (for example a benzyl radical); (iv) acycloalkyl radical comprising from 5 to 30 carbon atoms (ex.:cyclohexyl); (v) a —CH₂—C₆H₁₀—CH₂— radical; (vi) a —CH₂—C₆H₄—CH₂—radical; (vii) a CF₃ radical; (viii) a halogen atom; (ix) a hydroxylradical; (x) a carboxyl radical; (xi) an alkoxy radical OR′ where R′ hasa definition identical to that given in A1); (xii) a silyl group ═SiR₃R₄where n is between 0 and 12 and R₃ and R₄, which are identical ordifferent, represent a hydrogen atom, a hydroxyl radical, an alkoxyradical OR′ where R′ has a definition identical to that given in A1), alinear or branched alkyl radical comprising from 1 to 30 carbon atoms,an aryl radical comprising from 6 to 30 carbon atoms which is optionallysubstituted, a —C₆H₄—C(CH₃)₂—C₆H₄— radical or an alkenyl radicalcomprising from 2 to 12 carbon atoms. 99 to 1% by weight, and preferably99 to 40% by weight, of at least one polymerizable and/or at leastpartially polymerized organic matrix B comprising (co)monomers,(co)oligomers and/or (co)polymers selected from those having epoxy (α₁)and/or acrylate (α₂) and/or alkenyl ether (α₃) and/or hydroxyl (α₄)reactive functional groups (Brf), an effective amount of at least onecationic or cationic and radical initiator system C, optionally at leastone sensitizer D, and optionally at least one pigment E; (2) andpolymerization and/or crosslinking of the treated surface by itsexposure under a source of irradiation and/or under electron beam(s). 2.The process as claimed in claim 1, characterized in that the initiator Cis a cationic initiator, the anionic entity of which has the formula(x): [BX″_(a)R¹² _(b)]⁻  (X) in which: a and b are integers ranging from0 to 3 for a and from 1 to 4 for b, with a+b=4, the X″ symbolsrepresent: a halogen atom (chlorine or fluorine) with a=0 to 3, an OHfunctional group with a=0 to 2, the R¹² symbols, which are identical ordifferent, represent: a phenyl radical substituted by at least oneelectron-withdrawing group, such as, for example, OCF₃, CF₃, NO₂ or CN,and/or by at least 2 halogen atoms (very particularly fluorine), thisbeing when the cationic entity is an onium of an element from Groups 15to 17, a phenyl radical substituted by at least one electron-withdrawingelement or group, in particular a halogen atom (very particularlyfluorine), CF₃, OCF₃, NO₂ or CN, this being when the cationic entity isan organometallic complex of an element from Groups 4 to 10, an arylradical comprising at least two aromatic nuclei, such as, for example,biphenyl or naphthyl, which is optionally substituted by at least oneelectron-withdrawing element or group, in particular a halogen atom(very particularly fluorine), OCF₃, CF₃, NO₂ or CN, whatever thecationic entity.
 3. The process as claimed in the preceding claim,characterized in that the cationic entity of the cationic initiator isselected from onium salts of formula (VI):[(R¹⁰)_(n)-A-(R¹¹)_(m)]⁺  (VI) in which: A represents an element fromGroups 15 to 17, such as, for example: I, S, Se, P or N, R¹⁰ representsa C₆-C₂₀ carbocyclic or heterocyclic aryl radical, it being possible forsaid heterocyclic radical to comprise nitrogen or sulfur asheteroelements, R¹¹ represents R¹⁰ or a linear or branched C₁-C₃₀ alkylor alkenyl radical; said R¹⁰ and R¹¹ radicals optionally beingsubstituted by a C₁-C₂₅ alkoxy, C₁-C₂₅ alkyl, nitro, chloro, bromo,cyano, carboxyl, ester or mercapto group, n is an integer ranging from 1to v+1, v being the valency of the element A, m is an integer rangingfrom 0 to v−1, with n+m=v+1.
 4. The process as claimed in any one of thepreceding claims, characterized in that the organic matrix Aadditionally comprises poly-organosiloxanes A4), which are composed ofunits of formula (II) and are terminated by units of formula (III)and/or are cyclic and are composed of units of formula (II), whichformulae are represented below:

in which: the R⁶ and R⁷ symbols, which are alike or different,represent: a linear or branched alkyl radical comprising 1 to 8 carbonatoms which is optionally substituted by at least one halogen,preferably fluorine, the alkyl radicals preferably being methyl, ethyl,propyl, octyl and 3,3,3-trifluoropropyl, a cycloalkyl radical comprisingbetween 5 and 8 cyclic carbon atoms, which radical is optionallysubstituted, an aryl radical comprising between 6 and 12 carbon atoms,which radical can be substituted, preferably phenyl or dichlorophenyl,an aralkyl part having an alkyl part comprising between 5 and 14 carbonatoms and an aryl part comprising between 6 and 12 carbon atoms, whichpart is optionally substituted on the aryl part by halogens, alkylsand/or alkoxyls comprising 1 to 3 carbon atoms, the Z symbols, which arealike or different, represent: an R⁶ and/or R⁷ group, a hydrogenradical, and/or a crosslinkable oxetane functional group connected tothe silicon of the polyorganosiloxane via a divalent radical whichcomprises from 2 to 20 carbon atoms and which can comprise at least oneheteroatom, preferably oxygen, it being possible for the latter to bebonded directly to the silicon, forming an ≡Si—OC≡ bond, with at leastone of the Z symbols representing a crosslinkable oxetane functionalgroup.
 5. The process as claimed in any one of the preceding claims,characterized in that the matrix B comprises at least one of thefollowing organic species B1: (α₁) epoxides and noncycloaliphaticepoxides, (α₂) acrylates, (α₃) linear or cyclic alkenyl-ethers, and (α₄)and polyols.
 6. The process as claimed in the preceding claim,characterized in that the organic species B1 are chosen from thefollowing: α_(1.1)) cycloaliphatic epoxides, and in particular: epoxidesof the 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate type:

or bis(3,4-epoxycyclohexyl) adipate; α_(1.2)) noncycloaliphaticepoxides, and in particular: epoxides of the type of those resultingfrom the condensation of bisphenol A and of epichlorohydrin and of thetype: di- and triglycidyl ethers of bisphenol A alkoxylated with1,6-hexanediol, with glycerol, with neopentyl glycol and withtrimethylolpropane, or diglycidyl ethers of bisphenol A, alpha-olefinepoxides, Novolac epoxides, epoxidized soybean oil, epoxidized linseedoil and epoxidized polybutadiene, α₂) acrylates, and in particular:epoxidized acrylates, preferably the oligomer of bisphenol Aepoxydiacrylate (Ebecryl 600), polyester glycerol acrylates, preferablya mixture of oligomer of acrylate which is trifunctional obtained fromglycerol and polyester (Ebecryl 810), multifunctional acrylates,preferably pentaerythritol triacrylate (PETA), trimethylolpropanetriacrylate (TMPTA), 1,6-hexanediol diacrylate (HDODA),trimethylolpropane ethoxylate triacrylate, thiodiethylene glycoldiacrylate, tetraethylene glycol diacrylate (TTEGDA), tripropyleneglycol diacrylate (TRPGDA), triethylene glycol diacrylate (TREGDA) ortrimethylpropane trimethacrylate (TMPTMA), urethane acrylates, polyetheracrylates, polyester acrylates, unsaturated polyesters, acrylicacrylates, α₃) linear or cyclic alkenyl ethers and in particular: vinylethers, in particular dodecyl vinyl ether (DDVE), cyclohexyl vinyl ether(CVE), butanediol divinyl ether (BDVE), butanediol monovinyl ether(HBVE), cyclohexanedimethanol divinyl ether (CHDVE),cyclohexanedimethanol monovinyl ether (CHMVE), triethylene-glycoldivinyl ether (DVE-3) and vinyl ethers of formulae:

propenyl ethers, and butenyl ethers; α₄) polyols, and preferably thecompound of formula:


7. The process as claimed in any one of the preceding claims,characterized in that the organic matrix B additionally comprises atleast one monomer(s) and/or oligomer(s) and/or polymer(s) ofpolyorganosiloxane B2 nature, which monomer(s) and/or oligomer(s) and/orpolymer(s) are composed of units of formula (IV) and are terminated byunits of formula (V) or are cyclic and are composed of units of formula(IV), which formulae are represented below:

in which: the R⁶ and R⁷ symbols, which are alike or different, havedefinitions identical to those given for A4, the Z′ symbols, which arealike or different, represent: an R⁶ and/or R⁷ group, a hydrogenradical, and/or a crosslinkable organofunctional group, preferably anepoxy functional, dioxolane functional and/or alkenyl ether functionalgroup, connected at the silicon of the polyorganosiloxane via a divalentradical which comprises from 2 to 20 carbon atoms and which can compriseat least one heteroatom, preferably oxygen, with at least one of the Zsymbols representing a crosslinkable organic functional group.
 8. Theprocess as claimed in the preceding claim, characterized in that the(Brf)s of the polyorganosiloxane B are chosen from the followingradicals:

—(O)_(n′)—(CH₂)_(n″)—O—CH═CH₂, —(O)_(n′)—(CH₂)_(n″)—R⁸—O—CH═CH₂ and—(O)_(n′)—(CH₂)_(n″)—O—CH═CH—R⁹ in which: n′ represents 0 or 1 and n″ aninteger between 1 and 5 R⁸ represents: a linear, branched or cyclicC₁-C₁₂ alkylene radical which is optionally substituted, or a C₅-C₁₂arylene radical, preferably a phenylene radical, which is optionallysubstituted, preferably by one to three C₁-C₆ alkyl groups, and R⁹represents a linear or branched C₁-C₆ alkyl radical.
 9. A treatedplastic capable of being obtained by the process as claimed in any oneof the preceding claims.
 10. The plastic as claimed in the precedingclaim, characterized in that the surface treatment is carried out forthe purpose of forming a coating such as an ink, a nonstick coating, anadhesive coating or a varnish.